EP0748885B1 - Tiegel für die Züchtung fehlerfreier Einkristalle - Google Patents

Tiegel für die Züchtung fehlerfreier Einkristalle Download PDF

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Publication number
EP0748885B1
EP0748885B1 EP96304342A EP96304342A EP0748885B1 EP 0748885 B1 EP0748885 B1 EP 0748885B1 EP 96304342 A EP96304342 A EP 96304342A EP 96304342 A EP96304342 A EP 96304342A EP 0748885 B1 EP0748885 B1 EP 0748885B1
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EP
European Patent Office
Prior art keywords
crucible
vitreous silica
sidewall formation
bottom wall
crucibles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96304342A
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English (en)
French (fr)
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EP0748885A1 (de
Inventor
Richard L. Hansen
Robert D. Shelley
Larry E. Drafall
Robert M. Mccutchan
John D. Holder
Leon A. Allan
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SunEdison Inc
General Electric Co
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SunEdison Inc
General Electric Co
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Publication of EP0748885A1 publication Critical patent/EP0748885A1/de
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Publication of EP0748885B1 publication Critical patent/EP0748885B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting the melt
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002—Crucibles or containers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/213—SiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S65/00—Glass manufacturing
    • Y10S65/08—Quartz
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1032—Seed pulling
    • Y10T117/1052—Seed pulling including a sectioned crucible [e.g., double crucible, baffle]

Definitions

  • the present invention relates generally to crucibles for use in the preparation of silicon single crystals grown by the Czochralski process.
  • the invention particularly relates to a fused quartz crucible having one or more surfaces which have been treated with a devitrification promoter.
  • Single crystal silicon which is the starting material for most processes for the fabrication of semiconductor electronic components is commonly prepared with the so-called Czochralski process.
  • polycrystalline silicon (“polysilicon”) is charged to a crucible, the polysilicon is melted, a seed crystal is immersed into the molten silicon and a single crystal silicon ingot is grown by slow extraction.
  • the crucible of choice for use in the Czochralski process is commonly referred to as a fused quartz crucible or simply a quartz crucible and is composed of an amorphous form of silica known as vitreous silica.
  • vitreous silica One disadvantage associated with the use of vitreous silica, however, is the fact that contaminants on the inner surface of the crucible can nucleate and promote the formation of cristobalite islands in the vitreous silica surface (the islands being centered, in general, about the contamination site) as the polysilicon is - melted and the single crystal ingot is grown.
  • the cristobalite islands can be undercut and released as particles into the silicon melt, causing the formation of dislocations in the silicon ingot.
  • the cristobalite islands can be undercut, for example, by the action of a low melting eutectic liquid formed at the interface between the vitreous silica and cristobalite as described by Liu et al., "Reaction Between Liquid Silicon and Vitreous Silica,” J. Mater. Res., 7(2), p. 352 (1992).
  • Other mechanisms by which the cristobalite islands are undercut and released into the melt are also known in the art.
  • Crucibles formed from vitreous silica may also exhibit a loss of structural integrity when subjected to the extreme temperatures experienced during the melting of the polysilicon charge or the growth of the silicon ingot. In general, these crucibles soften with increasing temperature and are soft enough to easily flow under an applied stress when the crucible wall temperature exceeds 1817° K. Thus, graphite susceptors are frequently used to support the crucibles. Despite such reinforcement, however, quartz crucibles may buckle during the polysilicon melting and the crystal growth phases of the process, or when mechanical failure of the crystal puller occurs resulting in prolonged holding periods at high temperatures. Buckling occurs most often during remelt of an imperfect crystal or melting of bead polysilicon (i.e., granular polysilicon formed in a fluidized bed).
  • the ⁇ -cristobalite layer transforms to ⁇ -cristobalite.
  • the ⁇ -cristobalite to ⁇ -cristobalite phase transformations cause the devitrified surface to crack and form particulates on the surface. These particulates are released from the devitrified surface into the silicon melt, causing the formation of dislocations in the silicon ingot.
  • Japanese Kokai No. 52/038873 discloses the use of a xenon lamp to irradiate the inner crucible surface in order to remove electrostatically adhering metallic contaminants to reduce formation of oxidation induced stacking faults in a silicon single crystal.
  • Japanese Kokai No. 60/137892 describes a method of subjecting a crucible to electrolysis to remove alkali metals from the crucible which serves to reduce the incidence of lattice defects and crucible deformation.
  • U.S. Patent Nos. 4,956,208 and 4,935,046 describe crucibles having an opaque outer shell and an inner transparent quartz layer substantially free from bubbles for controlling the transfer of oxygen into a silicon melt.
  • the inner layer is also described as being effective in suppressing the growth of cristobalite at the crucible-melt interface, preventing the cristobalite from dropping off into the melt and disturbing growth of the crystal. Many of these treatments do not strengthen the walls of the crucible against deformation when subjected to severe temperatures, nor do they control the devitrification process in the presence of molten silicon.
  • U.S. Patent No. 4,102,666 describes the formation of a thin crystalline silica layer on the outer surface of a diffusion tube to improve its thermal dimensional stability.
  • the outer surface of the tube is treated with crystallization promoting nuclei such as oxides, carbides or nitrides of boron, aluminum, phosphorus, antimony, zinc, magnesium, calcium, gallium or Group IV elements of the Periodic Table.
  • the nuclei promote very slow devitrification which is said to increase the useful life of the diffusion tube.
  • the diffusion tubes are used in processing semiconductor wafers at temperatures of up to about 1300°C, i.e. temperatures which are significantly below the softening point of vitreous silica.
  • German Offenlegungsschrift No. 1,959,392 proposes protecting the inside wall of a quartz vessel with a substance which is inert at working temperatures, such as boron oxide.
  • European Patent Publication No. 0,463,543 A1 teaches a quartz glass crucible for use in a process for pulling a single crystal silicon having an outer layer containing less than 0.3 ppm each of sodium, potassium and lithium and more than 5 ppm of aluminum.
  • the outer layer further contains bubbles to present an opaque appearance.
  • a crucible having increased structural stability the provision of a crucible that releases less particulate contaminants into the silicon melt, and the provision of a crucible which provides improved yield and throughput of zero dislocation single crystals grown by the Czochralski process.
  • a crucible for the containment of molten silicon in a Czochralski process comprising a body of vitreous silica having a bottom wall and a sidewall formation extending up from the bottom wall and defining a cavity for holding the molten silicon, the sidewall formation and bottom wall each having an inner surface of vitreous silica and an outer surface of vitreous silica characterized in that the crucible comprises an alkaline earth metal devitrification promoter uniformly distributed on the inner vitreous silica surface of the sidewall formation of the crucible in a concentration between 0.10 mM/1000 cm 2 and 0.60 mM/1000 cm 2 and/or on the outer vitreous silica surface of the sidewall formation of the crucible in a concentration ranging from 0.10 mM/1000 cm 2 to 1.2 mM/1000 cm 2 , the distribution of the alkaline earth metal devitrification promoter on the inner vitreous silica
  • the invention further provides a crucible containing a charge of solid polysilicon, the crucible comprising a body of vitreous silica having a bottom wall and a sidewall formation extending up from the bottom wall and defining a cavity for holding the solid polysilicon, the sidewall formation and bottom wall each having an inner surface of vitreous silica and an outer surface of vitreous silica characterized in that the crucible comprises an alkaline earth metal devitrification promoter uniformly distributed on the inner vitreous silica surface of the sidewall formation of the crucible in a concentration between 0.10 mM/1000 cm 2 and 0.60 mM/1000 cm 2 and/or on the outer vitreous silica surface of the sidewall formation in a concentration ranging from 0.10 mM/1000 cm 2 to 1.2 mM/1000 cm 2 such that, during melting of the charge, the inner surface comprising the devitrification promoter in contact with the melt becomes uniformly devitrified on the inside of the crucible and/or
  • the present invention is directed to a crucible in which a semiconductor material is melted and held during a crystal growing.
  • the crucible includes a body of vitreous silica having a bottom wall and a sidewall formation extending up from the bottom wall and defining a cavity for holding the molten semiconductor material.
  • the sidewall formation has an inner and an outer surface.
  • An alkaline earth metal devitrification promoter may be distributed on the inner surface of the sidewall formation such that a first layer of substantially devitrified silica is formed on the inner surface of the crucible which is in contact with the molten semiconductor material when the semiconductor material is melted in the crucible during the crystal growing process.
  • An alkaline earth metal devitrification promoter may be distributed on the outer surface of the sidewall formation such that a second layer of substantially devitrified silica is formed on the outer surface of the crucible when the semiconductor material is melted in the crucible during the crystal growing process.
  • the first substantially devitrified silica layer is such that it promotes uniform dissolution of the inner surface and in so doing significantly reduces the release of crystalline silica particulates into the molten semiconductor material as a crystal is pulled from the molten semiconductor material.
  • the second substantially devitrified silica layer is such that it reinforces the vitreous silica body.
  • the first and second devitrified silica layers are substantially uniform and continuous.
  • the yield and throughput of dislocation-free silicon single crystals is significantly improved by uniformly coating at least one surface of a conventional fused quartz crucible with a devitrification promoter before the crucible is filled with silicon or otherwise used in a Czochralski process.
  • the deposited devitrification promoter provides nucleation sites on the surface of the crucible.
  • stable crystal seed nuclei form at these nucleation sites and the vitreous silica at the crucible surface crystallizes, forming a substantially uniform and continuous devitrified shell of ⁇ -cristobalite on the surface of the crucible.
  • the shell strengthens the crucible and maintains its shape.
  • the surface treated crucible does not deform or buckle because the devitrified shell has a melting point of about 2000° K, which exceeds both the maximum temperature employed in a Czochralski process and the softening point of vitreous silica (1817° K).
  • a substantially uniform and continuous devitrified shell formed on the inner surface of the crucible dissolves uniformly when in contact with a silicon melt. Dislocations formed in a growing crystal are thus minimized when an internally surface-treated crucible is used because ⁇ -cristobalite particles are not released into the melt by the devitrified shell.
  • FIG. 1 there is shown a crucible 10 having a bottom wall 12 and a sidewall formation 14 extending up from the bottom wall 12 and defining a cavity for holding molten semiconductor material.
  • the sidewall formation 14 and bottom wall 12 have respective inner surfaces 16, 18, and outer surfaces 20, 22.
  • An external coating 24 (not to scale) is on the outer surface 20 and forms a layer having a high density of nucleation sites which surrounds the exterior of the sidewall formation 14.
  • An internal coating 26 (not to scale) covers the inner surfaces 16, 18, forming a layer having a high density of nucleation sites covering the interior of the crucible 10. Coatings 24, 26 include a devitrification promoter.
  • the devitrification promoter reacts with the vitreous silica to form crystalline nuclei on the surfaces of the crucible.
  • a promoter containing barium reacts with vitreous silica to form crystalline nuclei on a crucible surface when the crucible is heated to a temperature in excess of about 600° C.
  • the silicon melt and the graphite susceptor act as a reducing agent and promote the rapid growth of these crystalline nuclei at the surface in a radial direction from the nucleation sites. In the presence of the silicon melt or the graphite susceptor, these crystalline nuclei grow to confluence, that is, a continuous ceramic shell is formed on the crucible.
  • devitrification promoters such as barium are released into the silicon melt where the promoters come into contact with the melt. The remainder of the devitrification promoter, however, remains adhered to the upper portion of the inner surface 16, forming a layer 28 which does not devitrify as shown in FIGS. 4 and 5.
  • the outer surface of the sidewall formation 30 comprises a devitrified surface 32
  • this surface reinforces the fused quartz crucible.
  • an inner devitrified surface 34 which forms on the portion of the sidewall formation 30 in contact with the silicon melt 36, inhibits the formation of melt borne crystalline silica particulates while growing a silicon single crystal.
  • the outer devitrified surface 32 and the inner devitrified surface 34 are layers of substantially devitrified silica.
  • substantially devitrified silica can be entirely composed of devitrified silica. Such a layer would be formed when the inner surface of the crucible is uniformly coated with the devitrification promoter.
  • the substantially devitrified silica can primarily contain devitrified silica with some exposed islands of vitreous silica in the otherwise continuous devitrified layer. Such a layer would be formed when minor portions of the inner surface of the crucible are not coated with the devitrification promoter during the coating process. Vitreous silica islands would not significantly contaminate the melt with crystalline particulates because the vitreous islands would not undermine the surrounding devitrified silica to cause it to be released into the melt.
  • the internal coating 26 (not to scale) covers the inner surface 16 of the sidewall formation 14.
  • the inner surface 18 of the bottom wall 12 is uncoated.
  • argon gas from the surrounding atmosphere is present between the silicon beads.
  • the argon gas becomes trapped at the crucible surface by the melt.
  • the bubbles are released and travel to the melt surface prior to crystal growth when the inner surface of the crucible is uncoated.
  • the bubbles are released into the melt during crystal growth and incorporated into the crystal as they reach the melt-crystal interface when the crucible has an inner coating on the sidewall formation 14 and bottom wall 12.
  • argon bubbles remain trapped within the melt on the coated bottom wall for a longer period of time because the coated surface has a higher surface tension than an uncoated bottom wall surface.
  • Argon gas entrapped within a growing crystal forms void defects in the crystal. It has been discovered that argon is not trapped in the crystal during crystal growth in large diameter (i.e., 45.72 cm (18 inch) and 55.88 cm (22 inch) diameter) crucibles if the inner surface 16 of the sidewall formation 14 is coated and the inner surface 18 of the bottom wall 12 remains uncoated.
  • the outer surface 20 of the crucible can be coated or uncoated.
  • argon bubbles are trapped in the crystal during crystal growth when the inner surfaces 16, 18 of the crucible are uncoated.
  • the outer surface 20 is preferably coated to prevent the small crucible from buckling.
  • the crucible 10 includes coatings 24, 26 as shown in FIGS. 1 and 2, zero dislocation yield and throughput are also improved when only the internal coating 26 or the external coating 24 is applied to the crucible. It is preferred that the outer surface 22 of the bottom wall 12 remains uncoated as shown in FIGS. 1 and 2. Coating the outer surface 22 increases the cost of the crucible without improving crucible performance.
  • the coatings 24, 26 each contain at least one devitrification promoter which provides crystal nucleation sites on the surfaces 16, 18, 20, 22 of the crucible 10.
  • Devitrification promoters suitable for coating the interior or exterior surfaces of the crucibles of the present invention include alkaline-earth metal oxides, carbonates, hydroxides, oxalates, silicates, fluorides, chlorides, and peroxides.
  • Some devitrification promoters such as titanium dioxide, zirconium dioxide, ferric oxide, ion pairs of an alkaline-earth metal cation and an organic anion including alkaline-earth metal formates, acetates, propionates, salicylates, stearates and tartrates, and promoters containing transition metals, refractory metals, lanthanides or actinides, can be used to coat the outer surfaces 20, 22 but not the inner surfaces because such promoters can cause crystal defects or reduce device lifetime if applied to the inner surfaces 16, 18 of a crucible.
  • the devitrification promoter is preferably an alkaline-earth metal selected from the group consisting of calcium, barium, magnesium, strontium and beryllium.
  • the alkaline-earth metal can be in any form which adheres to the crucible surfaces.
  • the alkaline-earth metal can be in the form of the element (e.g. Ba), a free ion (e.g. Ba 2+ ), or an ion pair with an anion such as an oxide, hydroxide, peroxide, carbonate, silicate, oxalate, formate, acetate, propionate, salicylate, stearate, tartrate, fluoride, or chloride.
  • the devitrification promoter is an oxide, hydroxide, carbonate or silicate of an alkaline-earth metal.
  • the coatings 24, 26 must contain sufficient devitrification promoter to nucleate a layer of substantially devitrified silica.
  • a concentration of at least about 0.10 mM of alkaline-earth metal per thousand square centimeters generally provides a uniform coating capable of promoting devitrification. If a weaker concentration is used, the nuclei may be too small to grow at a rate exceeding dissolution by the melt. Consequently, the nuclei are dissolved before crystallization occurs, particularly in a large diameter (e.g., 55.88 cm) crucible with a higher temperature melt at the crucible wall.
  • the concentration When the interior surface of a crucible is coated, the concentration must be low enough to prevent impurities within the coating composition from contaminating the melt and causing poor minority carrier lifetime and oxygen induced stacking faults.
  • the concentration of alkaline-earth metal deposited on the inner surface of the crucible ranges from 0.10 mM/1000 cm 2 to 0.60 mM/1000 cm 2 and, more preferably, ranges from 0.15 mM/1000 cm 2 to 0.30 mM/1000 cm 2 .
  • An externally coated crucible preferably has an alkaline-earth metal concentration ranging from 0.10 mM/1000 cm 2 to 1.2 mM/1000 cm 2 and, more preferably ranges from 0.30 mM/1000 cm 2 to 0.60 mM/1000 cm 2 .
  • the devitrification promoter most preferably has a segregation coefficient less than 2.25 x 10 -8 , indicating that the concentration of impurities within a grown crystal will be less than 0.05 parts per trillion atomic (2.5 x 10 9 /cm 3 ).
  • the most preferred devitrification promoter is barium, which is not readily incorporated in a growing crystal even when a considerable amount of barium is present within a silicon melt. Calcium can be an unsuitable devitrification promoter when used in coating the interior of a crucible because it is incorporated into a crystal at a higher concentration than barium at the same melt concentrations and can cause defects in the crystal.
  • the segregation coefficient of the devitrification promoter is insignificant because impurities on the crucible exterior generally do not affect the purity of the silicon single crystal.
  • the surface-treated crucibles of the present invention are prepared by applying a coating containing the devitrification promoter to a surface of a conventional fused quartz crucible.
  • Any fused quartz crucible that can be used in a Czochralski process can be surface-treated in accordance with the present invention.
  • Suitable crucibles are commercially available from manufacturers including General Electric Company and Toshiba Ceramics, or can be manufactured according to known methods, such as the method described in U.S. Patent No. 4,416,680.
  • Many commercially available crucibles have been treated to reduce the alkali metal concentration in the crucible. However, some of the crucibles have sodium, potassium and other alkali metals concentrated on their outer surfaces because of incomplete removal during treatment.
  • Alkali metals are preferably removed from the outside surface of a crucible before an external coating is applied to the crucible. If the alkali metals are not removed prior to applying the coating, the devitrified shell formed in accordance with the present invention may be separated from the crucible by a layer of low melting silicates. Devitrification proceeds very quickly as the crystal is grown and the crucible may buckle away from the devitrified shell.
  • a crucible surface can be coated by any method which deposits the devitrification promoter onto the surface, such as drip coating or spray coating processes.
  • a crucible is drip coated by dripping an aqueous or solvent based solution of a devitrification promoter onto the surface and decanting off the water or solvent after the promoter has adhered to the crucible surface.
  • an aqueous solution containing barium oxide, hydroxide, peroxide, carbonate, silicate, oxalate, formate, acetate, propionate, salicylate, stearate, tartrate, fluoride, or chloride devitrification promoter can be used to coat the crucible surface.
  • a suitable solution contains 2 mM barium hydroxide octahydrate per 21 ml water.
  • the solution is dripped onto the surface of the crucible as the crucible is rotated to distribute the solution evenly across the surface.
  • the barium hydroxide reacts with ambient or applied carbon dioxide gas to form the less soluble barium carbonate. Once the barium carbonate dries on the surface, the crucible can be stored for later use in a Czochralski process.
  • acid solutions or salt solutions can also be drip coated onto a crucible surface and the devitrification promoter can be precipitated onto the surface.
  • the crucible When the inner surface of the bottom portion of the crucible (as shown in FIGS. 2 and 3) is not to be coated, the crucible is positioned so that the solution will not drip onto the inner surface.
  • the entire inner surface of the crucible can be coated and the inner surface of the bottom portion can be etched with hydrochloric acid and water and then rinsed to remove the barium as barium chloride which is very soluble in water.
  • the drip coating method is preferred when treating the interior surface of a crucible because most of the impurities in the aqueous solution are decanted off and do not adhere to the crucible surface.
  • Another method for coating a crucible surface involves spraying a heated crucible with a solution containing a devitrification promoter to adhere the promoter to the crucible surface.
  • carbon dioxide gas and the barium hydroxide solution described above are simultaneously sprayed onto a crucible that has been heated to a temperature of 200 to 300°C.
  • the barium hydroxide immediately adheres to the crucible surface and is partially converted to barium carbonate upon contact with the carbon dioxide.
  • the surface is then simultaneously sprayed with water and carbon dioxide gas to complete the conversion of barium hydroxide to barium carbonate. Sufficient conversion is obtained once the pH of the coated surface is 9.5 or lower, preferably below about 8.
  • the spray coating method is preferred for coating the exterior of the crucible. Heating the crucible provides better adherence of the devitrification promoter and improves safety by reducing the risk of inhalation and ingestion of the promoter. A spray coated crucible also has a more uniformly coated surface and can be transported without the coating being abraded off during transit. Although the spray coating method generally introduces more impurities onto the surface, such contamination of the exterior of the crucible does not affect the purity of the silicon single crystal.
  • the crucible formed by either method is used in a Czochralski process
  • the crucible is filled with polysilicon and heated to melt the polysilicon.
  • the alkaline-earth metal devitrification promoter creates nucleation sites as the crucible is heated to the melt temperature.
  • barium carbonate becomes unstable as the crucible is heated and converts to barium oxide which readily reacts with silica on the crucible surface to form barium silicate.
  • the barium creates nucleation sites once the crucible is heated to about 600°C. Crystallization occurs at the nucleation sites as the silicate is heated, and continues throughout the crystal growth process, forming a ceramic shell on the crucible surface.
  • alkaline-earth metal hydroxide solution is preferred in coating crucibles of the invention
  • oxalate, oxide, peroxide, halide, propionate, salicylate, formate, acetate, stearate, tartrate, carbonate and silicate solutions can also be directly applied to the crucibles via the spray coating or drip coating methods. If an alkaline-earth metal carbonate or oxalate is applied to the surface, the carbonate or oxalate converts to an oxide as described above. The oxide then reacts with the silica crucible to form a silicate. The silicate crystallizes at the nucleation sites formed by the alkaline-earth metal or metal-oxide.
  • crucibles were prepared from commercially available vitreous quartz crucibles having a diameter of 35.56 cm (14 inches) and a height of 30.48 cm (12 inches). Each crucible was prepared by dripping an aqueous barium hydroxide solution onto the inner surface (i.e., the side and bottom portions) of the crucible as the crucible was rotated. Barium carbonate formed, separated from the solution, and coated the inner surface of the crucible. The excess solution was decanted off and the crucible was dried, resulting in a coating of about 2 mM barium on the inner surface of the crucible.
  • the surface-treated crucibles and standard crucibles were each charged with about 36 kg chunk polysilicon and 1.4 g of p-type dopant alloy and were then placed in standard crystal pullers available from the Hamco Division of Kayex Corporation. Each crucible was heated to about 1500°C until the polysilicon melted. A conventional Czochralski crystal pulling process was then initiated. The crucible began to rotate and the seed crystal was dipped into the melt. As the molten silicon began to crystallize onto the seed crystal, the seed was lifted at a rate sufficient to form a neck portion of the crystal. The pulling rate was then gradually decreased until the ingot diameter was about 152.4 mm (six inches). The pull rate was maintained until most of the silicon was consumed. Then, the pull rate and temperature were increased to form the tail end of the crystal ingot. The power supplied to the puller was then discontinued, the system was cooled, and the ingot was removed.
  • the crystals were analyzed to determine their zero dislocation length.
  • the zero dislocation length is the number of inches (or cm) of single crystal ingot which are pulled without dislocations in the crystal lattice.
  • the zero dislocation yield is the zero dislocation length per kilogram of polysilicon charged to the crucible prior to melt down.
  • Zero dislocation throughput is defined as the zero dislocation length per hours required to complete the run (i.e., the time ranging from set up of the system to obtaining a cooled crystal ingot).
  • Table 1 indicates the average zero dislocation length obtained during 43 runs using surface-treated crucibles in accordance with the present invention, and 44 runs using commercially available vitreous crucibles.
  • One run using a surface-treated crucible and six runs using standard crucibles are not considered in Table 1 because of power failure or unrelated process upsets.
  • two surface-treated crucible runs and one standard crucible run were eliminated because a zero dislocation loss occurred when a substantial melt remained in the crucible due to mechanical problems with the pulling apparatus. The grown crystal was withdrawn from the crystal puller and removed. A new seed was inserted into the melt and crystal growth was restarted.
  • Table 2 compares the zero dislocation yield and throughput for surface-treated crucibles and standard crucibles. Yield and throughput were improved by 17.5-24.6% and 15-21%, respectively, by internally treating the crucibles prior to use.
  • Table 2 Crucible Type Zero Dislocation Yield 2 (in/kg) [cm/kg] Zero Dislocation Throughput 2 (in/hr) [cm/hr] Internally Treated 124.6% [124.6%] 121% [121%] Standard 100% [100%] 100% [100%] Internally Treated 1 127.5% [127.5%] 124% [124%] Standard 1 110% [110%] 109% [109%] 1 Runs involving power failure or unrelated process upsets were eliminated. 2 Relative to standard crucible not adjusted for process upsets.
  • Externally surface-treated crucibles were prepared from commercially available vitreous quartz crucibles having a diameter of 55.88 cm (22 inches) and a height of 43.18 cm (17 inches). Each crucible was prepared by heating the crucible to 200-300°C and spraying carbon dioxide and an aqueous barium hydroxide solution (2 mM barium hydroxide octahydrate in 21 ml water) onto the outer surface (i.e., the side portion) of the crucible. Each crucible was spray cbated four times with the carbon dioxide and the barium hydroxide solution. The outer surface was then simultaneously sprayed with water and carbon dioxide to complete the conversion of barium hydroxide to barium carbonate until the pH of the coated surface was 9.5 or lower.
  • the zero dislocation yield for crystals grown from externally treated crucibles was 25.8% greater (98% confidence level) than the yield for crystals grown from standard crucibles.
  • Example 3 Partially Internally Surface-treated 55.88 cm Diameter Crucibles with Granular Polysilicon Charge
  • Example 4 Internally Surface-treated 35.56 cm Diameter Crucibles with Granular Polvsilicon Charge
  • Table 4 Crucible Charge Zero Dislocation Yield 1 (in/kg) Zero Dislocation Throughput 1 (in/hr) % Rejected Slices Standard Granular Polysilicon 100% (100%) 100% (100%) 0.19 Internally Treated 80% Granular/20% Chunk Polysilicon 102% (102%) 99% (100%) 1.55 Internally Treated Granular Polysilicon 97% (97%) 88% (88%) 2.28 1 Relative to standard crucible, granular polysilicon.
  • Example 5 Externally Surface-treated 35.56 cm Diameter Crucibles with Granular Polysilicon Charge
  • Two hundred forty externally surface-treated 35.56 cm diameter crucibles were prepared by drip coating the exterior side wall surfaces of a standard crucible with 10.5 ml of a 0.05 M barium hydroxide solution. Each crucible was loaded with 34 kg of granular polysilicon. One hundred twenty-nine internally surface-treated 35.56 cm diameter crucibles were prepared by drip coating the interior sidewall surfaces and bottom wall surfaces with 21 ml of a 0.1 M barium hydroxide solution. Each crucible was loaded with 24 kg of granular polysilicon and 10 kg of chunk polysilicon. After the polysilicon was melted, a single crystal ingot was pulled from the polysilicon melt within each crucible.
  • Table 5 Crucible Charge Zero Dislocation Yield 2 (in/kg) Zero Dislocation Throughput 2 (in/hr) Standard Granular Polysilicon Not Analyzed 1 [Not Analyzed 1 ] Not Analyzed 1 [Not Analyzed 1 ] Externally Treated Granular Polysilicon 100% [100%] 100% [100%] Internally Treated 70% Granular/30% Chunk Polysilicon 103% [103%] 98% [103%] 1 Three of five crucibles buckled during crystal growth. 2 Relative to externally treated, granular polysilicon.
  • Standard crucibles generally buckled during CZ crystal growth when charged with granular polysilicon. Such buckling was not observed when the crucibles were externally surface-treated. Crystals grown in the externally treated crucibles were also found to have significantly fewer voids as compared to crystals grown in the internally treated crucibles without a loss of zero dislocation yield or throughput in leaving the crucible interior untreated.
  • Example 1 Forty-eight standard 55.88 cm diameter crucibles were internally treated as described in Example 1. Sixteen of the crucibles were also externally treated as described in Example 2. Each of the crucibles was loaded with 100 kg of chunk polysilicon. Silicon single crystal 200 mm diameter ingots were grown via a conventional Czochralski method as previously described.
  • the relative zero dislocation yields for the internally surface-treated crucibles and the internally and externally surface- treated crucibles were 100% and 110%, respectively.
  • the zero dislocation yield was improved by about 9.8% by externally coating a crucible in addition to internal surface treatment.

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Claims (11)

  1. Tiegel für die Aufnahme von geschmolzenem Silizium in einem Czochralskiverfahren, wobei der Tiegel (10) einen Körper aus glasigem Silizium mit einem Boden (12) und einer sich von dem Boden (12) aufwärts erstreckenden Seitenwandausbildung (14) aufweist und einen Hohlraum zur Aufnahme des geschmolzenen Silizium begrenzt und die Seitenwandausbildung (14) und der Boden (12) jeweils eine innere Oberfläche (16, 18) aus glasigem Siliziumdioxid und eine äußere Oberfläche (20, 22) aus glasigem Siliziumdioxid haben, dadurch gekennzeichnet, dass der Tiegel (10) einen Erdalkalimetall-Entglasungspromotor aufweist, der auf der inneren glasigen Siliziumdioxidoberfläche (16) der Seitenwandausbildung (14) des Tiegels (10) in einer Konzentration zwischen 0,10 mM/1000cm2 und 0,60 mM/1000cm2 und/oder auf der äußeren glasigen Siliziumdioxidoberfläche (20) der Seitenwandausbildung (14) des Tiegels (10) in einer Konzentration in dem Bereich von 0,10 mM/1000cm2 bis 1,2 mM/1000cm2 gleichmäßig verteilt ist, wobei die Verteilung des Erdalkalimetall-Entglasungspromotors auf der inneren glasigen Siliziumdioxidoberfläche (16) und/oder auf der äußeren glasigen Siliziumdioxidoberfläche (20) der Seitenwandausbildung (14) der Art ist, dass eine erste Schicht aus im Wesentlichen entglastem Siliziumdioxid auf der inneren glasigen Siliziumdioxidoberfläche (16) und/oder auf der äußeren glasigen Siliziumdioxidoberfläche (20) des Tiegels (10) gebildet ist, wenn das Silizium in dem Tiegel (10) während des Czochralskiverfahrens eingeschmolzen wird, und wobei die erste im Wesentlichen entglaste Siliziumdioxidschicht der Art ist, dass sie auf der inneren Oberfläche der Seitenwandausbildung (14) die gleichförmige Auflösung der inneren Oberfläche und die Verringerung der Abgabe kristalliner Siliziumdioxidteilchen in das geschmolzene Silizium fördert, wenn ein Kristall aus dem geschmolzenem Silizium gezogen wird, und dass sie auf der äußeren Oberfläche der Seitenwandausbildung (14) den glasigen Siliziumdioxidkörper verstärkt.
  2. Tiegel enthaltend eine Charge aus festem Polysilizium, der einen Körper aus glasigem Siliziumdioxid mit einem Boden (12) und einer sich von dem Boden (12) aufwärts erstreckenden Seitenwandausbildung (14) aufweist und einen Hohlraum zur Aufnahme des festen Polysiliziums begrenzt, wobei die Seitenwandausbildung (14) und der Boden (12) jeweils eine innere Oberfläche (16, 18) aus glasigem Siliziumdioxid und eine äußere Oberfläche (20, 22) aus glasigem Siliziumdioxid haben, dadurch gekennzeichnet, dass der Tiegel (10) einen Erdalkalimetall-Entglasungspromotor aufweist, der auf der inneren glasigen Siliziumdioxidoberfläche (16) der Seitenwandausbildung (14) des Tiegels (10) in einer Konzentration zwischen 0,10 mM/1000cm2 und 0,60 mM/1000cm2 und/oder auf der äußeren glasigen Siliziumdioxidoberfläche (20) der Seitenwandausbildung (14) in einer Konzentration zwischen 0,10 mM/1000cm2 und 1,2 mM/1000cm2 gleichmäßig verteilt ist, so dass während des Einschmelzens der Charge die den Entglasungspromotor in Kontakt mit der Schmelze aufweisende, innere Oberfläche auf der Innenseite des Tiegels (10) gleichmäßig entglast und/oder während des Einschmelzens der Charge die den Entglasungspromotor aufweisende äußere Oberfläche (20) auf der Außenseite des Tiegels (10) gleichmäßig entglast.
  3. Tiegel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Entglasungspromotor auf der inneren Oberfläche (16) der Seitenwandausbildung (14) ist.
  4. Tiegel nach Anspruch 3, dadurch gekennzeichnet, dass der Entglasungspromotor einen Verteilungskoeffizienten in geschmolzenem Silizium von weniger als 2,25 x 10-8 hat.
  5. Tiegel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Entglasungspromotor auf der äußeren Oberfläche (20) der Seitenwandausbildung (14) ist.
  6. Tiegel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die innere Oberfläche (18) des Bodens (12) keinen Entglasungspromotor hat.
  7. Tiegel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Entglasungspromotor ein Erdalkalimetall aufweist, das unter Barium oder Strontium ausgewählt ist.
  8. Tiegel nach Anspruch 7, dadurch gekennzeichnet, dass der Entglasungspromotor Barium aufweist.
  9. Tiegel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die äußere Oberfläche (20) der Seitenwandausbildung (14) und die äußere Oberfläche (22) des Bodens (12) im Wesentlichen frei von Alkalimetallen sind.
  10. Tiegel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die innere Oberfläche (16) der Seitenwandausbildung (14) mit einem Erdalkalimetall in einer Konzentration zwischen 0,15 mM/1000cm2 und 0,3 mM/1000cm2 beschichtet ist.
  11. Tiegel nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die äußere Oberfläche (20) der Seitenwandausbildung (14) mit einem Erdalkalimetall in einer Konzentration zwischen 0,3 mM/1000cm2 und 0,6 mM/1000cm2 beschichtet ist.
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DE69615282T2 (de) 2002-04-18
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EP0748885A1 (de) 1996-12-18
CN1096506C (zh) 2002-12-18
CN1149634A (zh) 1997-05-14
US5976247A (en) 1999-11-02
KR970001603A (ko) 1997-01-24
TW366544B (en) 1999-08-11
KR100408905B1 (ko) 2004-04-13
JPH09110590A (ja) 1997-04-28
MY112218A (en) 2001-04-30
JP3046545B2 (ja) 2000-05-29

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